Solubilized phenyl mercury acetate compositions



United States Patent C SOLUBILIZED PHENYL MERCURY ACETATE COMPOSITIONS Joseph Fath, Morristown, George J. Leitner, lselin, and

Milton Nowak, Union, N. J., assignors, by mesne assignments, to Heyden Newport Chemical Corporation, a corporation of Delaware No Drawing. Application August 19, 1955 Serial No. 529,568

4 Claims. (Cl. 167-42) This invention relates to liquid compositions com prising phenyl mercury acetate and to methods of producing the same.

The use of organo-mercurial compounds as fungicides, bactericides, germicides, i. e., antimicrobials generally, has long been established. It has achieved great commercial importance in recent years due to the increasing awareness of the economic losses incurred annually through the microbial decomposition of cellulosic articles of commerce. More particularly, consumer goods, such as textiles, rope, rubber, paper, leather, paints, varnishes, lacquers and protective coatings generally, if not adequately protected, will, under conditions of prolonged Weathering and humidity, deteriorate rather rapidly due to attack by microorganisms, and the period of their usefulness will be foreshortcned considerably. The practice of protecting such articles with organo-mercurials, and more particularly, phenyl mercurics, has resulted in preventing their early and undue deterioration, thus effecting great annual consumer savings.

A number of phenyl mercurics have been heretofore employed, but by far the best, from both a functional standpoint and the standpoint of economics, is phenyl mercury acetate. However, this particular compound has presented a number of problems. For example, it is normally a solid and has a relatively low solubility in diluting media such as must be employed in connection with its use. In fact, its solubility in water is only approximately 1 part of the acetate to 600 parts of water and the magnitude of its solubility in organic solvents is substantially the same. Such being the case, commercial distribution and shipment of such concentrations involve altogether too much bulk, the greater proportion of which is solvent. There has been an urgent need for a phenyl mercury acetate product of high concentration and consequent minimum solvent content and one object of the present invention is to provide such a product whereby it is possible to produce concentrations of from 5%30% phenyl mercury acetate and even higher.

An important feature of this invention is that the phenyl mercury acetate products thereof in the concentrated form stated may be incorporated in the end products in which they are to be used by the simple act of stirring them.

Another disadvantage of phenyl mercury acetate compositions, as heretofore employed, is their lack of universal solubility. It has been heretofore necessary to prepare such compositions in accordance with the particular system in which they were to be used. 'If such an acetate were to be employed in an aqueous system, it was so constituted that it was useful only in such a system and the same was true with respect to phenyl mercury acetate useful in oil systems. Reissue Patent No. 23,863, dated August 31, 1954, is illustrative of phenyl mercury acetate capable of use only in aqueous systems. Hence another object of the invention is to produce what we may term a universal compound adapted for efficient and effective use in both types of systems.

An important feature of this invention is that its use is agents on an emulsified system is 2,824,825 Rammed 17' '5'?" 3. 9 5.

practically unrestricted in connection with the fungicide field and other fields where materials of this kindare useful and which involve oil or water vehicles. It may be noted in this connection that our tests have shown that when incorporated, for example, in oil vehicle paints which include metal drier catalysts, the presence of the products of this invention does not detrimentally affect or interfere with the drying performance of such catalysts. This fact is in marked contradistinction to the product set forth in Patent No. 2,423,121, issued July 1, 1947. That patent employs hydroxy alkyl amino compounds to etfect solubilization of reaction products with phenyl mercury acetate and is directed primarily for use of these products in aqueous systems. Experience has shown that if an attempt is made to employ them in oil systems, such as oil base paints, the hydroxy alkyl amino compounds have an extremely detrimental effect upon said catalysts and, as a matter of fact, effectually prevent oxidative film formation. Furthermore, when'used in aqueous systems such as latices, the cationic nature of these solutions very often interferes with the delicate colloidal system of the latex commonly produced by an anionic surfactant. The complete incompatibility and extremely detrimental effects of the use of anionic in the presence of cationic well recognized by those skilled in the art. 7 I

As a result of prolonged experimentation, research and tests, we have discovered that the aforesaid objects of this invention may be obtained by employing condensation products of alkylene oxides, more particularly, ethylene oxide, propylene oxide, butylene oxide, and certain reactants having at least one replaceable hydrogen atom, which may be utilized to solubilize phenyl mercury acetate in a manner essential to the performance of the functions stated.

Examples of compounds possessing the requisite hydrogen atom are: phenols, water-insoluble alcohols, fatty acids having at least 8 carbon atoms, water-insoluble amides having at least 8 carbon atoms, polyols, polyol esters, hydroxy esters, and water-insoluble mercaptans having at least 6 carbon atoms.

The compounds of this invention may be generally characterized by the formula wherein n is an integer greater than 1 and preferably between 2 and 50, R and R are selected from the group consisting of hydrogen and alkyl, X is derived from compounds having at least one replaceable hydrogen atom and selected from the group consisting of phenols, waterinsoluble alcohols, fatty acids having at least 8 carbon atoms, water-insoluble amides having at least 8 carbon atoms, polyols, polyol esters, hydroxy esters, water-insoluble mercaptans having at least 6 carbon atoms, and a represents the number of reactive hydrogen atoms in the compound from which X is derived.

The preferred compounds of our invention belong to the class of compounds wherein R and R are hydrogen atoms and are thus derived from ethylene oxide.

Specific examples of the compounds embraced within the above formula are the condensation products of an alkylene oxide and any one or more of the following, to wit: phenol, p-nonyl phenol, p-diisobutyl phenol, p-isobutyl phenol, p-tertiary amylphenol, decyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, stearyl alcohol, lauric acid, oleic acid, soya bean fatty acid, stearic acid,

palmitic acid, rosin fatty acids, lauramide, ,n-octadecanamide, n-octadecenamide, ethylene glycol, propylene gly monooleate sorbitantmonopalmitate, sorbitan trilinoleate, sorbitol hexastearate, glycerol monostearate, glycerol, dilaurate, tripropylene glycol monolaurate, pentapropylene cgiy'cols tfionostearatg caster: oil; buty-l 1 lactate, ethyl igly V colate;v ancttertiaryl dodeeyl mercaptanl. I 'Eortthe purpose ofpractical formulation, 'wehave found itzito be-of advantage at'times to use a. combination. of twoi on'm'ore; of: the; above compoundsand the use. of V a multiple, system of'alkylene oxide: condensatesoften maagentrasphenylimercury acetate: present 'i'nv the: compositionr Alowertratioof solubilizingagentrto phenyl mercury; acetate will notfnnction inithemanner stated.

1 'lheiendrproducts of .this invention maybe used in widely difierent:environments, utilizing any. of the foregoing vehicles whether, they be used as paint vehicles or diluents, depending upon the use to which the materials are to be put ,Examples-ofthe vehicles .or diluents .withw'hich compositionsofthis inventionare compatible. are: water, ethyl alcohol, isopropyl alcohol, jmineral spirits,tker'ose'ne, lins'eedoil, V. M. & P. naphtha, .XyloLtoluol, soya bean 'oil, a mineral oil, alkyd resin solutions ethylene glycol mono- .ethylethendioxane, ethylene glycol, etc. In fact, the end products1of1this1invention may be referred to as universal in-;their application to. ally systems andv vehicles used in paints, other filmrforming materials, and in other environments: where-phenylrmercury acetate hasrutility in the variousarts; i V V The following examples are illustrative of the composi tionsofthe present invention and the methods by which they are prepared a a v Example 1 A IntoQaiZOOcc. beakerwere'placed 90 guts. of the condensation products of mols; of ethylene oxide and 1 moleoflauramide; The compound was heated to 80C.

with agitation. At this temperature there were added 10 'gms. of phenyl mercury acetate and agitation was continued until complete solution had occurred. Upon cooling,

the solution remainedliquidand .free flowing and contained 10% solubilized phenyl mercury acetate.

7 Example 2 A Intoafldi) cc.;beaker were.placed 100.gms. of water and SSQJgmSmf .theicondens'ation product .of mols .ofethyl- V 'eneeoxideeand .1 ,moltof n-.octadecenamide.-' While -hea't-. inggand agitating; 50 guts; of phenyl mercury. acetate were.

suspended imthegsolution; After minutes at 75 C. a solution was obtained which, upon cooling, remained clear andcontained 10% solubilized phenyl mercury acetate.

Example 3 To gins. of the condensation-product of 1 mol of sorbitolandao'molsor ethylene oxide' in a 100 cc. beaker,

'there-w'ere-added 6.0 guts; of phenyl mercury acetate.

Heating to 80 and agitating-tor a period of '20 minutes fyielded a clear' solution. which, upon cooling to room 7 temperature, remained stable and yielded a composition a containing 13 phenyl mercury acetate.

I Exam plea 4 T645 of the rcondensation product .of ethylene: ox

ide and-i scn-lgitan monolanrate (marketed as .Twe'en 20,1 A tlas Po'wder Company), there were addedjgms. phenyl 'mercui'y aee'tate" at.85fC'.' Agitation for lO'minutes yielded a clearliqnidwhich, upon cooling; remainedimi vform. and; consisted of. a. phenyl mercury acetate.

T he mixture'was heated at ?;Ctf6i15 minutes Example 5 In 300 gms. of the esterrproduced by the condensation product of 1 mol of lauric acid and9 mols of ethylene oxide, there were suspendedSO of phenyl'ine'rcury acetate with thorough agitation; Heating'was begun and when a temperature of F. was obtainedsolutiogof the mercury compound-became complete. The ;resulting' composition contained 143% solubilized phenylmercury acetate. 7 I a Example 6 Into a 100 cc. beaker there wereplaced 25 gms. of the condensation product of 1 mol of oleic acid and 25 mols of ethylene oxide, 20' gms; of ethylene glycol and 5 gms. of water. The mixture was agitated to uniformity and, at F., there were dissolved 5 gms'; 'o f'phehyl men cury acetate. The resultingclearsolution cofitain'e'd wfi, phenyl mercury acetate. 1

p Example 7 i '7 7 To 45 gms. ofthe ester produced by the coil of l8 mols of ethylene oxide and 1 acids (marketed'as ReneX 20,? Atlas Powder. Compa there were added'5 gins. of pheiiylmercury acetate; atlSQf' c. Agitation for 10 minutes res'ulted 'in a. cla'n iqtiia product containing" 10% solfibiliiedipheriyl mercury acerate. A

' Exam les To 45 gms. of the condensationiproduct ofil rnol" f nonyl phenoland 2O mols of ethyleneoiridezatrGS there were'added-o' gms; :ofphenylmercury;acetates Agi tating atrthis temperature resulted-in aaclearrsolution irr 20 minutes. Upon cooling, a: stable compositioircontaina ing 11; 7%- phenyl'mercury, acetate -was;:obtained2 I Example 9 5 gms, of phenyl. mercury acetate; were addegl to 2Q. gm. of the condensate: of 15. mols-of ethylene pgtideand 1 mol'of lauryl alcohol condensate at .7 5 Crwithaceorm panied agitation. A stable compositioncontaining-20% phenyl mercury acetate wasobtained on cooling:

Example 10 7 To 45 gms; of the condensation'products 'ofslimoluof Castor oil with l5 mols of. ethylene oxide there-'werez added 7 gms. of phenyl mercury, acetate. Theiyniixtur'e was agitated andheated to 80. :C. Afterfl'fminuteszaa solution was obtained which, uponcooling,1remained:clan and contained 13.4% solubilized phenyl mercury acetate:

7 Exampleii I T0 45 gms; of thenoni'onid' surfactant preau 1 the'eondensa'tion' at '1 mole of-pheml' with 20' 'ni ethylene oxide there; were added 6*gms5 of pliehy curyac'etate'at 75 'C; Heatingat 75 T6 80" CI to "10 minutes resulted in a clear, stable solution containing 11.7% phenyl mercury acetatew ExampleJZ;

To 40 gms. of "the polyoiiyetliyleriesorbitolf 6f: lauric and ioleic acids (marketed as AfloX 1Q45A-ff1 i I Powder Company), there were adddat.'80 '-CT,..\'vitH accompanied agitation, 1O gms. of phenylmerciii'y acetate. After ZOTminutes of agitation'at this temperaturea st l solution containing 20% phenylmercury aeetatawa ou Y tained. a

v 'E xamplei13 (1 oxide; there wereadded Tg'ms'iofl phenyl cur'yaee a'clear solution'containing'13".4% hen l-mercur al rate.

Example 14 To 40 gms. of di-propylene glycol monolaurate there were added gms. of phenyl mercury acetate with accompanied agitation. The mixture was heated at 85 90 C. for 5 minutes to produce a clear, homogeneous product, containing phenyl mercury acetate. This composition was readily diluted with aromatic type solvents to give stable dilution.

Example 15 10 gms. of phenyl mercury acetate were dissolved in a mixture of gms. of the condensation product of 1 mol of paratertiary octyl phenol and 15 mols of ethylene oxide and 20 gms. of the condensation product of 1 mol of tall oil fatty acids and 18 mols of ethylene oxide by heating and stirring for 10 minutes at 80 C. The resulting solution containing 18.2% phenyl mercury acetate can be diluted with water or aromatic solvents.

Example 16 7 gms. of phenyl mercury acetate were readily dissolved in gms. of the condensation product of 1 mol of phenol and 5 mols of propylene oxide by heating at -80 C. for 15 minutes. The resulting composition contained 13.4% phenyl mercury acetate.

Example 17 To 35 gms. of the condensation product of 1 mol of rosin fatty acids and 20 mols of ethylene oxide, there were added 15 gms. of phenyl mercury acetate with agitation. Upon heating this mixture for 15 minutes at C., a product containing 30% phenyl mercury acetate was obtained.

The products of each of the foregoing examples were thoroughly tested and found to be compatible with the several vehicles hereinbefore referred to, proving that the end products of this invention are universal in their application.

In these tests the solubilized phenyl mercury acetate was simply poured into and stirred in the vehicle in order to incorporate it. In every case it was found to be stable in such vehicle and there was no appreciable precipitation noted even after prolonged periods of standing.

The products of the present invention, because of their compatibility with the vehicles referred to, enter into solution, in the majority of cases, so that they are more readily available to carry out their functions in practice and do not settle out. Furthermore the applied material in the vehicle is of uniform application throughout because the material and the Vehicle constitute, in effect,

a homogeneous solution, all parts of which are uniform. Such being the case, there is every indication from experiments already undertaken that a homogeneous solution of phenyl mercury acetate made in accordance with the present invention has a higher efliciency as a fungicide,

or end uses of the product. This is particularly true Where pest control presents special problems and requires exceptionally large amounts of economic poisons to properly protect against mildew and other destructive organisms.

In some instances we may, if desired, add to the cornpositions of our invention minor amounts of compounds which tend to raise the pH of the system to above 7. Traces of ammonium hydroxide, for example, may sometimes be used advantageously in combination with the present compositions. We wish it understood, however, that this is not essential to the present invention.

The foregoing detailed description sets forth the invention in its preferred practical forms, but the invention is to be understood as fully commensurate with the appended claims.

Having thus fully described the invention, what we claim as new and desire to secure by Letters Patent is:

1. A composition of matter comprising phenyl mercury acetate solubilized by being -in commingled state with a non-ionic surface active compound having the formula t wherein n is an integer greater than 1 and less than 50, R and R are selected from the group consisting of hydrogen and alkyl having 1-2 carbon atoms, X is derived from compounds having at least one replaceable hydrogen atom and selected from the group consisting of phenols, waterinsoluble alcohols, fatty acids having at least 8 carbon atoms, polyols, polyol esters, hydroxy esters, water-insoluble mercaptans having at least 6 carbon atoms, and a represents the number of reactive hydrogen atoms in the compound from which X is derived, said composition being a non-aqueous homogeneous solution containing 5%30% of phenyl mercury acetate and %70% of said compound.

2. A composition according to claim 1, wherein the alkylene oxide is ethylene oxide.

3. A composition according to claim 1, wherein the alkylene oxide is propylene oxide.

4. A non-aqueous composition of matter comprising a homogeneous solution of phenyl mercury acetate and a condensation product of ethylene oxide and tall oil fatty acids there being at least twice as much condensation product as there is phenyl mercury acetate in the solution.

References Cited in the file of this patent UNITED STATES PATENTS Dinerstein May 5, 1953 OTHER REFERENCES 

1. A COMPOSITION OF MATTER COMPRISING PHENYL MERCURY ACETATE SOLUBILIZED BY BEING IN COMMINGLED STATE WITH A NON-IONIC SURFACE ACTIVE COMPOUND HAVING THE FORMULA 